Process for the rapid fixing of ethylene by means of sulphuric acid for the purpose of obtaining ethyl sulphuric esters



Patented Mar. 2, 1926.

UNITED STATES PATENT OFFICE.

AUGUSTIN AMEDEE LOUIS JOSEPH DAMIENS, OF ABCUEIL-QAOHAN, MARIE CHARLES I JOSEPH ELISEE 1m LOISY, or PARIS,

PIETTE, OF BRUSSELS, BELGIUM.

FRANCE, AND OLIVIER JOSEPH GISLAIN PROCESS FOR THE RAPID FIXING OF ETHYLENE IBY MEANS OF SULI'HURIO ACID FOR THE PURPOSE OF OBTAINING ETHYL SULPHURIC ESTERS.

No Drawing.

To all whom it may concern:

Be it known that we, AUeUs'rIN AMEnEE LOUIS J osnrn DAMIENS, of Arcueil-Cachan, Seine, France, MARIE. CHARLES JOSEPH 5 ELISEE DE Lorsr, of Paris, France, and

OLIVIER JosErH GIsLAm PIE'r'rE, of Brussels, Belgium, have invented a process for the rapid fixing of ethylene by means of sulphuric acid for the purpose of obtaining ethyl sulphuric esters, of which the followingis a clear and exact description.

It is well known that ethylene is absorbed by sulphuric acid and that according to the ceous matters, to the detriment of ethyl sul-- phuric acid, formation, besides the latter, of its'isomer: isethionic acid, the proportion of which increases as the temperature becomes higher and higher and which has up to now no industrial application.

2. Pressm"e.l3y increasing the pressure of the ethylene gas, the rate of its fixing on sulphuric acid is proportionally increased, but considerable pressures must be reached for obtainin a sufiicient rate of reaction;

moreover this process, applicable to pure.

ethylene or to gases rich in ethylene, is not 40 industrially applicable when ethylene is to be trapped from complex gases containing only a small proportion of the same.

3. UataZg zers.It has also been proposed to use certain bodies, such as vanadic anhydride, uranyl sulphate, tungstic and molybdic acids, acting as catalyzers, that is to say accelerating by their presence the rate of fixing of ethylene by sulphuric acid, but the researches made by the applicants have shown that with the above mentioned cataor neutral ethyl sulphate Application filed April 13, 1922. Serial No. 552,306.-

lyzers only infinitely small quantities of ethyl sulphuric esters are formed and that the main products of the reaction are entirely different bodies.

These various processes allow therefore to obtain only a very small proportion of ethyl sulphuric acid and for this reason it has not been possible to use them industrially.

The present invention has for its object a process permitting the rapid fixing of ethylene by sulphuric acid and practically allowing to obtain only sulphuric esters C H SO, (ethyl sulphuric acid) and (O,H ,),,SO, .(neutral ethyl sulphate), without formation of isomers or foreign bodies. 65

This process is essentially characterized by the use of a catalyzer composed of iron, copper, or equivalent common metal; containing the metal under its smallest valency, for instance a ferrous compound FeSO (and not a ferric compound such as Fe ($0 a cuprous compound (and not a cu vric compound), such as sub-chloride 0 copper Cu cl sub-oxide of copper Cu O, sub-sulphate of copper 1 30,, etc., or any compounds capable of giving them birth, for instance, copper sulphate CuSO and a reducing body which will transform it into cuprous sulphate Cu SO,,.

During the reaction of sulphuric acid on ethylene in presence of the above mentioned catalyzer the temperature must be maintained between 0 and 50 (3., and the preferregl temperature range is between 15 and 50 5' At the end of the operation, ethyl sulphuric acid and neutral ethyl sulphate (both soluble in. concentrated sulphuric acid) are obtained. The neutral ethyl sulphate separates by coming to the surface of the liquid when the acid is diluted, any rise of temperature being avoided,

The relative proportions of ethyl sulphuric acid and neutral ethyl sulphate obtained by this process vary according to the conditions under which the operation is carried out, and according to the degree of concentration of the sulphuric acid used and to the temperature at which the reaction is effected, it will be possible to obtain at. will 100 one or the other of these ethyl sulphuric esters.

In case it is desired to obtain principally ethyl sulphuric acid C H HSO ordinary sulphuric acid of 66 Baum is used, that is tosay containing 92- to 95% of acid H and the temperature most favorable for the reaction, is from to C.

This process presents the main following advantages:

1. The absorption of ethylene is effected with great rapidit and owing to the low temperature at which the process is carried out, the sulphuric acid does not substantially exert any detrimental action on the products formed. p

2. The catalyzing body used is a common and cheap product.

3. This catalyzing body is insoluble in sulphuric acid, which difi'erentiates it from the catalyzers used up to this day which were soluble. The considerable advantages connected with this property are, on the one hand, that the greater division of the acid is promoted by the presence in its mass of a precipitate in suspension and, on the other hand, that the catal zer can easily be collected at the end of t e o eration, by decantation, filtration or centri uging, and be used over again for subsequent reactions,

For carrying out the present process in the case of its application to the trapping of ethylene contained in industrial gases; natural gas, gas from the distillation of fuels (coke oven gas, illuminating gas, cracking gas, schist gas, synthetic ethylene, atci); it is desirable first to free these gases om benzol and ammonia, to dehydrate them and, generally speaking, to free them from products which might be objectionable on 'account of their action either on the acid or on the catalyzing body (hydrocarbons of the acet lene and ethylene series, homologues of ethy ene, sulphurated compounds, etc.).'

The reagent fixing the ethylene (sulphuric acid to which is added the catalyzing body) is, after absorption, subjected to decautation,

- filtration or centrifuging, so that the catalyzether, and distillation.

ing body can be collected and can be returned to the circulation after or without purification.

v The production of alcohol or ether by means 0 ethyl sulphuric acid obtained by the present process is carried out by th'e prdinary methods: dilution of this acid -in a eater or less proportion of water, according as it is desired to produce alcohol or By means of the present process the fixing of ethylene by sulphuric acid is rapidly efi'ecte at ord'nary temperature a'n the neutral ethyl sulphate begins to form when the acid reaches a concentration .in acid sul-v phate or ethyl sulphuric acid which is only of 25.6% instead of 7 5% in the old process.

The final output is therefore very considerand we desire the claims to be interprete as covering such equivalents.

Claims 1. A process for the rapid fixing of ethylene by sulphuric acid for the purpose of the industrial roduction of sulphuric esters C H SO, ethyl sulphuric acid) and (C HQ SO (neutral ethyl sulphate), which consists: in adding to sulphuric acid of about 66 Baum, as catalyzer, a cuprous compound containing copper in the monovalent state, in causing a gaseous current containing ethylene to pass through this acid, maintaining during the reaction a temperature of from 0 to 50 G.separating the catalyzer from the acid, diluting the latter, and collecting, on the one hand the neutral ethyl sulphate which floats t0 the surface of the sulphuric acid and, on the other hand, the ethyl sulphuric acid which remains in solution in this acid.

2. A. process for the rapid fixing ofethylene by sulphuric acid for the purpose of the industrial production of sul huric esters C H SO (ethyl sulphuric aci and (C I-I SO (neutral ethyl sulphate), which consists: in adding to sulphuric acid of about 66 Baum, as catalyzer, sub-oxide of copper Cu O, in causing a gaseous current containing ethylene to pass through this acid, maintaining during the reaction a temperature of from 0 to 50 0., separating the catalyzer from the acid, diluting the latter, and collecting onthe one hand the neutral ethyl sulphate which floats to the surface of the sulphuric acid and, on the other hand, the ethyl sulphuric acid which remains in solution in this acid.

3. A process for the rapid fixingof ethylene by sulphuric acid for the purpose of obtaining principally ethyl sulphuric acid, which consists: in adding, as catalyzer, to ordinary concentrated sulphuric acid of about 66 Baum, a cuprous compound cofftaining copper in the monovalent state, in causing a gaseous current containing ethylene to pass through this acid, maintaining during the reaction the temperature maintaining during the reaction the temsulphuric acid for the purpose of obtaining perature between 15 and' 50 C.-and in ethyl sulphuric ethers, signed by us this 22 collecting the sulphuric eolution which conday of March, 1922. 5 g g iiga fifiggfiig traces only Aucus'rm AMEDEl-l LOUIS JOSEPH DAMIENS. The foregoing specification of our process MARIE, CHARLES JOSEPH J3EE for the rapid fixing of ethylene by means of OLIVER JOSEPH GISLAIN PIETTE- 

